Ammonia is synthesized using electrochemical and non-electrochemical reactions. The electrochemical reactions occur in an electrolytic cell having a lithium ion conductive membrane that divides the electrochemical cell into an anolyte compartment and a catholyte compartment. The catholyte compartment includes a porous cathode closely associated with the lithium ion conductive membrane. The overall electrochemical reaction is: 6LiOH+N2→Li3N (s)+3H2O+3/2O2. The nitrogen may be produced by a nitrogen generator. The non-electrochemical reaction involves reacting lithium nitride with water and/or steam as follows: Li3N (s)+3H2O→3LiOH+NH3 (g). The ammonia is vented and collected. The lithium hydroxide is preferably recycled and introduced into the anolyte compartment. The electrolytic cell is shut down prior to reacting the lithium nitride with water. The cathode is preferably dried prior to start up of the electrolytic cell and electrolyzing Li+ and N2 at the cathode.